Photographic element comprising a bleach accelerator releasing compound

ABSTRACT

A color photographic element is disclosed comprising a support bearing at least one photographic silver halide emulsion layer, an image dye-forming coupler, and a coupler (A) capable of forming a compound that is washed out of the photographic element upon processing and capable of releasing a bleach accelerator group, wherein the coupler (A) is represented by the formula: 
     
         (SOL).sub.x --COUP--(R.sup.1).sub.y --(R.sup.2).sub.z --BLEACH.

This invention relates to new photographic couplers, such as naptholicand acylanilide couplers, that are capable of forming washout dyes andreleasing bleach acclerator groups in a photographic material uponphotographic processing for formation of an improved image and to aphotographic material and process using such compounds.

Various ways are known in the photographic art for release of aphotographically useful group (PUG) from a compound, such as aphotographic coupler, in a photographic material and process. Forexample, U.S. Pat. Nos. 4,248,962; 4,409,323 and 4,861,701 describesgroups that enable timed release of a photographically useful group.Bleach accelerator groups have also been used as coupling-off groups,such o as described in European Patent Specification No. 193389 and U.S.Pat. Nos. 4,861,701; 4,959,299 and 4,912,024.

The part of the compound that remains in the photographic material afterrelease of the coupling-off groups and the dye that is formed in thematerial from the reaction with oxidized developer often provideundesired properties in the photographic material during or afterphotographic processing. For example, the dye formed from a coupler uponrelease of the coupling-off group often adversely affects the desiredimage. One answer to this problem has been to provide awater-solubilizing group on the parent coupler to enable the dye formedfrom the coupler to be washed out of the photographic element uponphotographic processing. Such couplers are described in, for example,U.S. Pat. Nos. 4,482,629 and 5,026,628.

A class of washout couplers (couplers capable of forming dyes that maybe washed out of photographic materials containing such couplers uponphotographic processing) that are especially useful is the naphtholicclass of couplers, such as described in U.S. Pat. Nos. 4,482,629 and5,026,62. However, such couplers have not provided both enabling ofwashout of the dye formed and bleach acceleration upon processing of thephotographic material containing such a coupler.

The present invention solves this problem by means of a colorphotographic element comprising a support bearing at least onephotographic silver halide emulsion layer, an image dye-forming coupler,and a bleach accelerating releasing coupler, (BARC), coupler (A) capableof forming a compound that is washed out of the photographic elementupon processing or forms a compound that washes out after furtherreaction; wherein, the coupler (A) is represented by the formula:

    (SOL).sub.x --COUP--(R.sup.1).sub.y --(R.sup.2).sub.z --BLEACH

wherein;

SOL is a water solublizing group;

SOL is known in the photographic art such as described in U.S. Pat. No.5,026,628. The water solublizing group can be selected from such groupsas carboxyl, sulfo, and hydroxyl groups which may also form a salt asdescribed in U.S. Pat. No. 4,482,629 and is of sufficient hydrophilicityto impart good alkali solubility to the dye formed by the couplingreaction with an oxidized product of a color forming developing agentwith the coupler (A). Preferred SOL groups are --CONH₂, --CONHCH₃, --CO₂H and --OH;

COUP is a coupler moiety, such as a cyan, magenta or yellow dye formingcoupler moiety;

R¹ is selected from a timing group and a releasing group;

R² is selected from --OC(O)--, --OC(S)--, --SC(O)-- and --SC(S)--;

BLEACH is a bleach accelerator group that is capable of being releasedupon processing;

x is 1, 2, or 3; and

y and z individually are 0, 1 or 2.

Such couplers enable not only the washout of dyes formed from thecoupler during photographic processing but also the acceleration ofbleaching of the silver formed during processing. Couplers of theinvention can be coated in imaging layers, non-imaging layers orinterlayers. Non-imaging layers or interlayers can contain interlayerscavengers, filter dyes of any type known in the photographic artincluding solid particle dispersion, conventional oil-in water dispersedfilter dyes and washout filter dyes, non-imaging silver emulsions suchas fine particle Carey-Lea or Lippmann emulsion containing layers, oryellow colored silver emulsions which are non-imaging layers. Theinterlayers can be located between imaging layers, between non-imaginglayers, between an imaging and an non-imaging layer, between anantihalation layer and an interlayer or between an antihalation and animaging layer. In addition to releasing a bleach accelerator group, saidcouplers behave as photographic scavengers, forming washout dyes, andpreventing excess oxidized color developer from diffusing to anotherimaging layer. Further, when coated in an imaging or non-imaging layer,these couplers can affect the development inhibition of the silverhalide in not only the layer in which it is coated but also in adjacentlayers thus allowing for the use of increased amounts of developmentinhibiting releasing compounds in photographic elements, resulting inincreased sharpness. Further, one particular advantage of locating saidcouplers in an interlayer is to minimize any speed loss due to directcompetition of oxidized color developer for said couplers over theimaging couplers.

The coupler moiety can be any coupler moiety that enables formation of adye during photographic processing that can be washed out of thephotographic material containing such a coupler. A preferred COUP is anaphtholic coupler moiety containing a water solubilizing group attachedto a group in the 2-position of the naphtholic coupler moiety. Any watersolubilizing group known in the photographic art is useful. Preferredwater solubilizing groups include carboxyl, sulfo, hydroxyl,sulfonamido, carbonamido, sulfamoyl, carbamoyl and salts thereof. Amidegroups such as --CONH₂ and CONHCH₃ are especially useful.

A preferred coupler (A) is a naphtholic coupler comprising a watersolubilizing group in the 2-position and represented by the formula:##STR1## wherein: (R¹)_(y) --(R²)_(z) --BLEACH is a coupling-off groupwherein

R¹ is selected from a timing group and a releasing group;

R² is selected from --OC(O)--, --OC(S)--, --SC(O)-- and --SC(S)--;

BLEACH is a bleach accelerator group;

y and z individually are 0, 1 or 2;

R⁴ can be selected from hydrogen, or a substituent such as --Cl, --NO₂,--OCH₃, --NHSO₂ R⁵, --NHCOR⁵, --SO₂ NHR⁵, --CONHR⁵, --CO₂ R⁵, or --COR⁵and which does not adversely affect the release of (R¹)_(y) --(R²)_(z)--BLEACH from COUP;

R³ and R⁵ is selected from the group consisting of hydrogen, substitutedor unsubstituted alkyl containing 1-5 carbon atoms and substituted orunsubstituted aryl containing 6-8 carbon atoms wherein the substitutedor unsubstituted alkyl or aryl is a solublizing group or contains asolublizing group;

at least one of R¹ and R² contains a photographic ballast; and

w is 0, 1, 2 or 3.

A preferred R¹ group is selected from the group consisting of: ##STR2##wherein; Q is selected from O (oxygen), S (sulfur), or N (nitrogen);

R⁶ and R¹⁰ is hydrogen or a substituent selected from substituted orunsubstituted alkyl and substituted or unsubstituted aryl, nitro,hydrogen, amino, substituted amino, carboxylic acid, sulfonic acid,methoxy, chloro, bromo, ester groups such as --CO₂ CH₃, keto groups suchas --COCH₃, or --NHCOCH₃, --CONHCH₃, --NHSO₂ CH₃, or --SO₂ NHCH₃ ;

R⁷, R⁸, R¹¹, and R¹² are selected from hydrogen, substituted orunsubstituted alkyl, and substituted or unsubstituted aryl;

R⁹ is unsubstituted or substituted alkyl or substituted or unsubstitutedaryl;

Z¹ represents the atoms necessary to complete a 5 or 6 member aryl orheterocyclic group;

n is 0, 1 or 2; and

at least one of R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹ and R¹² contains a photographicballast.

R¹ groups useful in the invention are described in U.S. Pat. No.4,886,736 incorporated herein by reference. Specific R¹ groups can befound at Col. 16, line 50 through Col. 21 and preferably contain aballast.

A preferred R² group is: ##STR3## A further preferred coupler (A) is anaphtholic coupler selected from the group having the followingformulae: ##STR4## wherein R² through R¹², w, n, Q, and Z¹ are asdefined previously. BLEACH as referred to herein can be represented bythe formula:

    --S--R.sup.13 --R.sup.14

wherein:

R¹³ is an unsubstituted or substituted alkylene containing 1 to 8carbons atoms; and

R¹⁴ is a water solubilizing group.

The following are useful examples of R¹³ groups: ##STR5##

The following R¹⁴ groups are examples of useful water solublizinggroups: ##STR6## wherein: R^(14a) is hydrogen or alkyl of 1 to 4 carbonatoms,

R^(14b) is alkyl of 1 to 4 carbon atoms and wherein at least one ofR^(14a) and R^(14b) is alkyl and the total carbons in R^(14a) andR^(14b) is no more than 8. R^(14a) and R^(14b) together can form a ring.

Preferred couplers (A) are represented by the structures denoted as:B-1, B-5, B-6, B-7, B-8, B-9, B-10, B-11, B-12, B-18, B-19, B-20, B-21,B-22, and B-23.

The coupling off group as described can be any group or combination ofgroups that is releasable during photographic processing and enablesrelease, with or without time delay, of BLEACH, a bleach acceleratorgroup, used in the acceleration of bleaching of silver in thephotographic material. Especially useful coupling-off groups aredescribed in U.S. Pat. Nos. 4,912,024; 4,959,299 and European PatentSpecification No. 193389, the disclosures of which are incorporatedherein by reference.

Herein the term coupler refers to the entire compound including thecoupler moiety and the coupling-off group. The term coupler moietyherein refers to that portion of the compound other than thecoupling-off group.

The timing groups as described, when such a group is employed in thecoupling-off group, can be any timing group or combination of timinggroups known in the photographic art. Such timing groups enabletailoring of the timing of release of the bleach accelerator group atthe appropriate time and place. Useful timing groups are described in,for example, U.S. Pat. Nos. 4,959,299; 4.861.701; 4,912,024; 4,409,323;and 4,248,962 and European Patent Specification No. 193389, thedisclosures of which are incorporated herein by reference.

The releasing groups as described, when such a group is employed in thecoupling-off group, can be any releasing group or combination ofreleasing groups known in the photographic art. Such releasing groupsdiffer from the described timing groups in that the o releasing groupsdo not provide a significant time delay in the release of a contiguousor adjacent group.

The water solubilizing group (SOL) can be any water solubilizing groupknown in the photographic art to enable wash-out of the dye formed inphotographic processing from the compound (A). Typical water-solublizinggroups include groups terminated with an acid group, such as carboxy,sulfo or hydroxy which may also form a salt and other groups describedin U.S. Pat. No. 4,482,629 (col. 4, lines 1-3) or an amide group. Thecompound (A) can have one or more water-solubilizing groups. The numberand type of water-solubilizing groups should not be sufficient to makethe compound (A) mobile in the photographic element prior to exposureand processing. The (R¹)_(y) --(R²)_(z) --BLEACH can also contain one ormore water-solubilizing groups if desired.

A typical water-solubilizing group (SOL) is carbonamido group--CONHR_(a) wherein R_(a) is hydrogen or an alkyl group containing 1 to3 carbon atoms, preferably --CONHCH₃ or --CONHC₂ H₅ ; or a groupcontaining a water-solubilizing group, such as carboxy, sulfo or hydroxygroups, for instance, --CONH₂ CH₂ CH₂ OH, --CONH₂ CH₂ CO₂ H, or --CONH₂CH₂ CH₂ CO₂ H. Such a group can be, for example, in the 2-position ofthe naphtholic coupler.

During photographic processing, the reaction of coupler (A) withoxidized color developing agent cleaves the bond between thecoupling-off group and the coupler moiety of the coupler (A). Tailoringof the particular parts of the releasing groups and timing groups asrequired for a given releasable bleach accelerator group allows controlover the timing and rate of the release of the bleach accelerator group.

The releasing group and/or timing groups can contain a ballast group,BALLAST, if desired. As used herein BALLAST is a ballast group that isknown in the photographic art. The ballast group as described is anorganic group of such size and configuration as to confer on themolecule sufficient bulk to render the molecule substantiallynon-diffusible from the layer in which it is coated in a photographicelement. Representative ballast groups include substituted orunsubstituted alkyl or aryl groups typically containing 8 to 40 carbonatoms.

A process of forming an image having the described advantages comprisesdeveloping an exposed photographic element by means of a colordeveloping agent in the presence of described coupler (A).

The naphtholic coupler moiety can be ballasted or unballasted providedthat the dye formed upon oxidative coupling is capable of being washedout of the photographic element. It can be monomeric, or it can be partof a dimeric, oligomeric or polymeric coupler, in which case more thanone group containing the bleach accelerator group can be contained inthe coupler, or it can form part of a bis compound in which the bleachaccelerator group forms part of a link between two coupler moieties.

The photographic element can comprise other couplers known in thephotographic art. The photographic element can, for example comprise atleast one photographic coupler that is capable of release duringphotographic processing a reagent or a photographic dye. A photographicreagent herein is a moiety that upon release further reacts withcomponents in the photographic element, such as a development inhibitor,a development accelerator, a bleach inhibitor, a bleach accelerator, acoupler (for example, a competing coupler, a dye-forming coupler, or adevelopment inhibitor releasing coupler (DIR coupler), a dye precursor,a dye, a developing agent (for example, a competing developing agent, adye-forming developing agent, or a silver halide developing agent), asilver complexing agent, a fixing agent, an image toner, a stabilizer, ahardener, a tanning agent, a fogging agent, an ultraviolet radiationabsorber, an antifoggant, a nucleator, a chemical or spectral sensitizeror desensitizer.

The bleach accelerator group can be present in the coupling-off group asa preformed species or it can be present in a blocked form or as aprecursor. The PG,13 bleach accelerator group can be for example apreformed bleach accelerator group or the bleach accelerator functioncan be blocked.

There follows a listing of patents and publications that describerepresentative couplers useful in the a photographic material of theinvention:

I. Couplers

A. Couplers which form cyan dyes upon reaction with oxidized colordeveloping agents are described in such representative patents andpublications as: U.S. Pat. Nos. 2,772,162; 2,895,826; 3,002,836;3,034,892; 2,474,293; 2,423,730; 2,367,531; 3,041,236; 4,333,999 and"Farbkuppler-eine Literaturubersicht," published in Agfa Mitteilungen,Band III, pp. 156-175 (1961).

Preferably such couplers are phenols and naphthols which form cyan dyeson reaction with oxidized color developing agent.

B. Couplers which form magenta dyes upon reaction with oxidized colordeveloping agent are publications as: U.S. Pat. Nos. 2,600,788;2,369,489; 2,343,703; 2,311,082; 3,152,896; 3,519,429; 3,062,653;2,908,573 and "Farbkuppler-eine Mitteilungen," Band III, pp. 126-156(1961).

Preferably such magenta dye-forming couplers are pyrazolones orpyrazolotriazole couplers.

C. Couplers which form yellow dyes upon reaction with oxidized and colordeveloping agent are described in such representative patents andpublications as: U.S. Pat. Nos. 2,875,057; 2,407,210; 3,265,506;2,298,443; 3,048,194; 3,447,928 and "Farbkuppler-eine Mitteilungen,"Band III, pp. 112-126 (1961).

Preferably such yellow dye-forming couplers are acylacetamides, such asbenzoylacetamides and pivaloylacetamides.

D. Couplers which form colorless products upon reaction with oxidizedcolor developing agent are described in such representative patents as:U.K. Patent No. 861,138; U.S. Pat. Nos. 3,632,345; 3,928,041; 3,958,993and 3,961,959.

The naphtholic couplers of the invention are especially useful incombination with at least one development inhibitor releasing coupler(DIR couplers) known in the photographic art.

The photographic couplers of the invention can be incorporated inphotographic elements by means and processes known in the photographicart. In a photographic element prior to exposure and processing thephotographic coupler should be of such size and configuration that itwill not diffuse through the photographic layers.

Photographic elements of this invention can be processed by conventionaltechniques in which color forming couplers and color developing agentsare incorporated in separate processing solutions or compositions or inthe element.

Photographic elements in which the compounds of this invention areincorporated can be a simple element comprising a support and a singlesilver halide emulsion layer or they can be multilayer, multicolorelements. The compounds of this invention can be incorporated in atleast one of the silver halide emulsion layers and/or in at least oneother layer, such as an adjacent layer, where they will come intoreactive association with oxidized color developing agent which hasdeveloped silver halide in the emulsion layer. The silver halideemulsion layer can contain or have associated with it, otherphotographic coupler compounds, such as dye-forming couplers, coloredmasking couplers, and/or competing couplers. These other photographiccouplers can form dyes of the same or different color and hue as thephotographic couplers of this invention. Additionally, the silver halideemulsion layers and other layers of the photographic element can containaddenda conventionally contained in such layers.

A typical multilayer, multicolor photographic element can comprise asupport having thereon a red-sensitive silver halide emulsion unithaving associated therewith a cyan dye image-providing material, agreen-sensitive silver halide emulsion unit having associated therewitha magenta dye image-providing material and a blue-sensitive silverhalide emulsion unit having associated therewith a yellow dyeimage-providing material, at least one of the silver halide emulsionunits having associated there with a photographic coupler of theinvention. Each silver halide emulsion unit can be composed of one ormore layers and the various units and layers can be arranged indifferent locations with respect to one another.

The light sensitive silver halide emulsions can include coarse, regularor fine grain silver halide crystals or mixtures thereof and can becomprised of such silver halides as silver chloride, silver bromide,silver bromoiodide, silver chlorobromide, silver chloroiodide, silverchlorobromoiodide and mixtures thereof. The emulsions can benegative-working or direct-positive emulsions. They can form, latentimages predominantly on the surface of the silver halide grains orpredominantly on the interior of the silver halide grains. They can bechemically and spectrally sensitized. The emulsions typically will begelatin emulsions although other hydrophilic colloids are useful.Tabular grain light sensitive silver halides are particularly usefulsuch as described in Research Disclosure, January 1983, Item No. 22534,and U.S. Pat. No. 4,434,226.

The support can be any support used with photographic elements. Typicalsupports include cellulose nitrate film, cellulose acetate film,polyvinylacetal film, polyethylene terephthalate film, polycarbonatefilm and related films or resinous materials as well as glass, paper,metal and the like. Typically, a flexible support is employed, such as apolymeric film or paper support. Paper supports can be acetylated orcoated with baryta and/or an a-olefin polymer, particularly a polymer ofan a-olefin containing 2 to 10 carbon atoms such as polyethylene,polypropylene, ethylene-butene copolymers and the like.

The coupler (A) can be used in photographic elements in the same way asphotographic couplers which release bleach accelerator groups havepreviously been used in photographic elements.

Depending upon the nature of the particular PUG, the couplers can beincorporated in a photographic element for different purposes and indifferent locations.

In the following discussion of suitable materials for use in theemulsions and elements of this invention, reference will be made toResearch Disclosure, December 1978, Item 17643, published by IndustrialOpportunities Ltd., Homewell Havant, Hampshire, P09 1EF, U.K., thedisclosures of which are incorporated herein by reference. Thispublication will be identified hereafter by the term "ResearchDisclosure".

The photographic elements can be coated on a variety of supports asdescribed in Research Disclosure Section XVII and the referencesdescribed therein.

Photographic elements can be exposed to actinic radiation, typically inthe visible region of the spectrum, to form a latent image as describedin Research Disclosure Section XVIII and then processed to form avisible dye image as described in Research Disclosure Section XIX.Processing to form a visible dye image includes the step of contactingthe element with a color developing agent to reduce developable silverhalide and oxidize the color developing agent. Oxidized color developingagent in turn reacts with the coupler to yield a dye.

Preferred color developing agents useful in the invention arep-phenylene diamines. Especially preferred are4-amino-N,N-diethylaniline hydrochloride;4-amino-3-methyl-N,N-diethylaniline hydrochloride;4-amino-3-methyl-N-ethyl-N-β-(methanesulfonamido)ethylaniline sulfatehydrate; 4-amino-3-methyl-N-ethyl-N-β-hydroxyethylaniline sulfate;4-amino-3-β-(methanesulfonamido)-ethyl-N,N-diethlaniline hydrochloride;and 4-amino-N-ethyl-N-(2-methoxyethyl)-m-toluidine di-p-toluenesulfonicacid.

The described photographic materials and processes can be used withphotographic silver halide emulsions and addenda known to be useful inthe photographic art, as described in, for example, Research Disclosure,December 1989, Item No. 308,119, the disclosures of which areincorporated herein by reference

With negative working silver halide the processing step described abovegives a negative image. To obtain a positive (or reversal) image, thisstep can be preceded by development with a non-chromogenic developingagent to develop exposed silver halide, but not form a dye, and thenuniformly fogging the element to render unexposed silver halidedevelopable. Alternatively, a direct positive emulsion can be employedto obtain a positive image.

Development is followed by the conventional steps of bleaching, fixing,or bleach-fixing, to remove silver and silver halide, washing anddrying.

Compounds as described can be prepared by reactions and methods known inthe organic compound synthesis art. The following descriptionillustrates these syntheses:

General Synthesis--Routes A and B

Compounds of the invention can be prepared by two routes, A and B asfollows:

In route A, Scheme 1, the BLEACH G-1, is reacted with phosgene to formthe thiochloroformate G-2 which is then reacted with the alcohol groupof coupler G-3, in the presence of a weak base to give compounds of theinvention, G-4. If G-4 contains an ester group on R¹⁴, or anotherblocked solublizing group, an additional final step is necessary to formthe free solublizing group. Examples of the synthesis of compounds ofthe invention using route A are given for B-1, B-7 and B-8.

In route B, Scheme 2, the alcohol group of coupler G-3 is reacted withphosgene to form the chloroformate G-5, which in the presence of astrong base is reacted with the BLEACH to give compounds G-4, of theinvention. As before, if the solublizing group R¹⁴ was blocked duringthe synthesis, a final step would remove this blocking group. Examplesof the synthesis of compounds of the invention using route B are givenfor B-1, B-5, B-6, B-7 and B-8. ##STR7##

SYNTHESIS OF INVENTION COMPOUND B-1--ROUTE A Compound 1

Phenyl-1,4-dihydroxy-2-naphthoate, (100 g, 356.78 mMol) was dissolved indeoxygenated tetrahydrofuran, (500 mL) and deoxygenated methanol, (500mL) added. To this solution, stirred at room temperature under anitrogen atmosphere, was added ammonium acetate, (50.0 g, 648.63 mMol)followed by concentrated ammonium hydroxide, (1.0 L). After stirring for3 hr. the reaction solution was then poured into ice-cold 2N-HCl, (4.0L) and enough concentrated HCl added to bring the pH to 1. The resultingproduct, Compound (1), was filtered off, washed well with water andair-dried. The crude product was washed with dichloromethane andair-dried again. Yield: 62.0 g (72%).

Compound (2)

Compound (1), (50.0 g, 0.246 Mol) was dissolved in dry pyridine, (150mL) and acetonitrile (75 mL) added. The solution was stirred and cooledto -5° to 0° C. Ethyl chloroformate, (50 mL, 0.523 Mol) was then addeddropwise with stirring while maintaining the temperature at 0° C. Afterthe addition, the cooling bath was removed and the temperature allowedto reach room temperature. The reaction mixture was then graduallyheated to reflux and the solvent allowed to distill off. This procedurewas continued until the temperature had risen to approximately 120° C.and 150 mL of solvent had been collected. Heating under reflux wascontinued for an additional 1 hr period. The reaction mixture was thencooled to approximately 50° C. and poured into 2N-HCl, (3.0 L) held atroom temperature. This suspension was stirred for approximately 15 min.filtered, and the residue washed well with water, acetonitrile, andfinally ether. This gave the product, Compound (2), sufficiently purefor the next step. Yield: 43.5 g (77%).

Compound (3)

Compound (2), (23.0 g, 100.35 mMol) was taken up in deoxygenateddimethyl sulfoxide, (250 mL) and deoxygenated water, (25 mL) added. Tothis solution, stirred at room temperature under nitrogen, was added 85%potassium hydroxide, (9.9 g, 150.53 mMol) and stirring continued untildissolution, approximately 15 min. Then 4-chloro-3-nitrobenzaldehyde,(18.62 g, 100.35 mMol) was added all at once and the resulting solutionstirred at 60° C. for 1 hr. The reaction mixture was then poured intoice-cold 2N-HCl, (2.0 L) and filtered off. The product, Compound (3),was washed with water and, while still wet, slurried in methanol,filtered and washed with ether. This product was pure enough to be usedin the next step. Yield: 28.0 g (74%)

Compound (4)

Compound (3), (28.0 g, 74.01 mMol) in a powdered form was suspended intetrahydrofuran, (150 mL) and methanol, (100 mL). Water, (100 mL) wasadded, followed by sodium borohydride, (2.8 g, 74.01 mMol) in smallportions. More tetrahydrofuran, (50 mL) was added to aid stirring. Atthe end of the sodium borohydride addition, complete dissolution hadbeen achieved. The reaction was allowed to proceed for a further 15 min.then poured into ice-cold 2N-HCl, (2.0 L) and the product filtered off.The product was washed with methanol and, while still wet, with solvent,suspended in ethanol and heated to reflux. The solution was cooled,filtered, washed with methanol, ether and finally air-dried. A secondcrop of material was obtained on concentrating the mother liquor. Totalyield of the hydroxymethyl derivative of compound (3), 19.5 g (67%). Thehydroxymethyl derative of compound (3), (19.0 g, 50 mMol) was suspendedin water, (200 mL) containing 85% potassium hydroxide, (26.34 g, 400mMol). To this mixture was added methanol, (50 mL), and this was heatedto 80° C. for 1 hr. The resulting dark yellow-brown solution was cooledand poured into ice-cold 2N-HCl, (2.0 L). The yellow product, compound(4), was filtered off, washed well with water and air-dried. Yield: 17.7g (100%).

Compound (5)

Compound (4), (17.7 g, 50 mMol) was dissolved in tetrahydrofuran, (80mL) and methanol, (300 mL) added. Raney-Nickel which had been washedseveral times with water and then methanol was added and the solutionhydrogenated at 55 psi for 2 hr. After this period hydrogen uptake hadceased. The catalyst was filtered off, washed with methanol, and thefiltrate concentrated under reduced pressure to give the product, theamino derative of compound (4 ). This product was deemed sufficientlypure to be carried on to the next step. Yield: 100%). The amino derativeof compound (4), (50.0 mMol) was dissolved in dry pyridine, (150 mL) andhexadecylsulfonyl chloride, (16.2 g, 50.0 mMol) was added. The solutionwas stirred at room temperature under a nitrogen atmosphere for 30 min.The pyridine was concentrated under reduced pressure and the residuetaken up in ethyl acetate. This ethyl acetate solution was then washedwith 2N-HCl (×3), dried (MgSO₄), filtered and concentrated. Theresultant residue crystallized from acetonitrile. After filtering,washing with acetonitrile and drying, the yield of product, compound(5), amounted to 16.3 g, (53% calculated from compound (4)).

Methyl 3-[(chlorocarbonyl)thiol]propionate (6)

Methyl 3-thiopropionate, (11.5 mL, 0.104 mMol) was dissolved intetrahydrofuran, (100 mL) and the solution cooled to 0+ C. A20%-solution of phosgene in toluene, (205 mL, 0.415 Mol) was added in asteady stream, whereupon the temperature rose to approximately 10° C.After the phosgene had been added the cooling bath was removed and thereaction stirred for 8 hrs. and let warm to room temperature. At the endof this period the solvent and excess phosgene were removed underreduced pressure and the residual viscous liquid co-evaporated withdichloromethane, (X3). The product, methyl3[(chlorocarbonyl)thiol]propionate, (6) so obtained was used directly inthe next step.

Compound (7)

Compound (5), (36.4 g, 59.3 mMol) was dissolved in tetrahydrofuran, (200mL) and methyl 3[(chlorocarbonyl)thio]propionate, (6), (19.0 g, 103.8mMol) in tetrahydrofuran, (30 mL) added slowly over a period ofapproximately 15 mins. When all of the 3[(chlorocarbonyl)thio]propionatehad been added, pyridine, (14.4 mL, 178.0 mMol) was added in a steadystream. The resulting reaction mixture was stirred at room temperaturefor 24 hrs. At the end of this period, the solvent from the reactionmixture was concentrated under reduced pressure and the residue taken upin ethyl acetate. The ethyl acetate solution was then washed with 2N-HCl(×3), dried (MgSO₄), filtered and the solvent removed under reducedpressure. The resulting oil was dissolved in a solvent mixture of ethylacetate/dichloromethane/heptane in the ratio 20:10:70 and pressurechromatographed using this solvent system. The first major band wascollected. Yield: compound (7), 21.0 g, 47%.

Invention B-1

Compound (7), (3.0 g, 4.0 mMol) was dissolved in acetic acid, (30 mL)and concentrated hydrochloric acid, (approximately 10 mL) graduallyadded so that the former did not come out of solution. The reactionsolution was then stirred at room temperature for 48 hrs. At the end ofthis period the acetic acid was removed from the reaction under reducedpressure and the residue dissolved in ethyl acetate. The ethyl acetatesolution was then washed with 2.5%-Na₂ CO₃ (×2), 2N-HCl (×1), dried(MgSO₄), filtered and concentrated to an oil. This oil was dissolved ina solvent mixture of ethyl acetate/heptane/acetic acid in the ratio of40:60:1 and pressure chromatographed using the same solvent mixture. Thefirst major band was collected to give the invention compound, (I-1).Yield: 2.0 g, 67%. Calculated for C₃₈ H₅₂ N₂ O₉ S₂.2CH₃ COOH: % C, 8.31;% H, 6.99; % N, 3.24; and % S, 7.41. Found: % C, 58.44; % H, 6.64; % N,3.52; and % S, 7.79. ##STR8##

SYNTHESIS OF INVENTION COMPOUND B-7--ROUTE A Ethyl2-[(chlorocarbonyl)thiol]acetate (6a)

Ethyl 2-[(chlorocarbonyl)thiol]acetate (6a), was prepared from ethylthioacetate in a similar way to Methyl3-[(chlorocarbonyl)thiol]propionate (6).

Compound (7a)

Compound (7a) was prepared in a similar manner to that of compound (7).

Invention B-7

Compound of the invention B-7,route A, was prepared from (7a) in asimilar manner to that of invention compound B-1 from compound (7).##STR9##

SYNTHESIS OF INVENTION COMPOUND B-8--ROUTE A2-[(Chlorocarbonyl)thiol]ethyl propionate (6b)

2-[(Chlorocarbonyl)thiol]ethyl propionate (6b), was prepared from2-thioethyl propionate in a similar way to methyl3-[(chlorocarbonyl)thiol]propionate (6).

Compound (7b)

Compound (7b) was prepared in a similar manner to that of compound (7).

Invention B-8

Compound of the invention B-8, was prepared from (7b) in a similarmanner to that of invention compound B-1 from compound (7). ##STR10##

SYNTHESIS OF INVENTION COMPOUND B-1--ROUTE B Compound (8)

Compound (5) (2.5 g, 4.08 mMol), was dissolved in tetrahydrofuran (20mL) and treated with a solution of phosgene in toluene (5 mL of a 20%solution, 10.20 mMol). The resulting solution was stirred at roomtemperature for 2 hours and then concentrated under reduced lo pressureat room temperature. The resulting oil, without further purification wastaken on to the next step.

Compound (9)

Compound (8) as described above (4.08 mMol), was dissolved intetrahydrofuran (20 mL), to which was then added 2-thioethyl acetate(1.36 mL, 12.24 mMol) followed by N,N-diisopropylethylamine (2.1 mL,12.24 mMol) and the resulting solution stirred at room temperature for 2hours. At the end of this period the reaction solution was concentratedunder reduced pressure, dissolved in ethyl acetate and the ethyl acetatesolution washed with 2N-HCl (×3), dried (MgSO₄), filtered and thefiltrate concentrated under reduced pressure. The residual oil, withoutfurther purification was taken on to the next step.

Invention B-1

Compound of the invention B-1, was generated from compound (9) ontreating (9) with concentrated hydrochloric acid in acetic similar tothe generation of B-1 from compound (7). ##STR11##

SYNTHESIS OF INVENTION COMPOUND B-5--ROUTE B Compound (8)

Compound (5), (25.0 g, 40.8 mMol) was dissolved in tetrahydrofuran, (200mL) and the solution cooled in an ice-bath. A 20%-solution of phosgenein toluene, (50.4 mL, 102 mMole) was added with stirring, at such a rateto keep the temperature in the range of 0°-10° C. After the addition thetemperature was allowed to warm to room temperature over a 2 hr. period.After this period the reaction solution was concentrated to an oil underreduced pressure with the application of the minimum amount of heating.The residual oil was taken on to the next step.

Invention B-5

To a stirred solution of 3-diethylaminoethanethiol hydrochloride, (9.0g, 53.0 mMole), in water, (150 mL) was added sodium carbonate, (8.6 g,81.1 mMole). To this solution was added ethyl acetate, (200 mL) and withgood stirring compound (8), (40.8 mMol) in ethyl acetate, (50 mL) wasadded slowly. The two phase solution was stirred at room temperature for1 hr. At the end of this period the ethyl acetate layer was separatedfrom the aqueous layer and the former washed with water (×1), 2N-HCl(×2), dried (MgSO₄), filtered and concentrated under reduced pressure.The residue was dissolved in a 35% solution of ethyl acetate in heptaneand pressure chromatographed. The first major band was collected to givecompound (I-2). Yield: 10 g, [(32%), calculated from compound (5)].

C₄₁ H₆₁ N₃ O₇ S₂ : M⁺ 771.

H¹ --NMR(CDCL₃): δ=8.44(m, 1H, Ar), 7.78(m, 1H, Ar), 7.57(m, 3H, Ar),7.02(s, 1H, Ar), 6.95(d, 1H, Ar),

6.57(d, 1H, Ar), 6.26(br. s, 2H, --NH₂), 5.12(s, 2H, benzylic --CH₂ --),3.24(br. t, 2H, --NHSO₂ CH₂ --), 2.93(m, 2H, --SCH₂ CH₂ N--), 2.69(m,2H, --SCH₂ CH₂ N--), 2.55(q, 4H, --NCH₂ CH₃), 1.90(m, 2H), 1.42(m, 2H),1.25(s, 24H), 1.02(t, 6H, --NCH₂ CH₃), 0.88(t, 3H). ##STR12##

SYNTHESIS OF INVENTION COMPOUND B-6--ROUTE B Invention B-6

Compound (8), (40.8 mMol) was dissolved in tetrahydrofuran, (100 mL) and3-morpholinoethanethiol, (6.6 g, 44.9 mMole) in tetrahydrofuran, (30 mL)was added at a fairly rapid rate. The resulting reaction was stirredovernight and then concentrated to an oil under reduced pressure. Theresidual oil was dissolved in ethyl acetate and the ethyl acetate washedwith 2N-HCl (×2), dried (MgSO₄), filtered and concentrated to an oil.This oil was dissolved in a 30% solution of ethyl acetate indichloromethane and pressure chromatographed using the same solventsystem to remove some impurties. The product, compound (I-3), was elutedfrom the column on changing to a 50% solution of ethyl acetate indichloromethane.

Yield: 7.0 g, (25%).

C₄₁ H₅₉ N₃ O₈ S₂ : M⁺ 785.

H¹ --NMR(CDCL₃): δ=8.41(m, 1H. Ar), 7.75(m,1H, Ar), 7.59(m, 3H, Ar),7.42(br. s, 1H, NH), 7.02(s, 1H, Ar), 6.95(d, 1H, Ar), 6.55(d, 1H, Ar),6.4(br. s, 2H, NH₂), 5.12(s, 2H, benzylic --CH₂ --), 3.59(m, 4H, --OCH₂CH₂ N--), 3.25(br. t, --NHSO₂ CH₂ --), 2.97(t, 2H), 2 55(t, 2H), 2.41(m,4H, --NCH₂ CH₂ O--), 1.92(m, 2H), 1.42(m, 2H), 1.2(s, 24 H), 0.88(t,3H). ##STR13##

SYNTHESIS OF INVENTION COMPOUND B-7--ROUTE B Compound (7a)

Compound (8) (16.3 mMol), was dissolved in tetrahydrofuran (100 mL) andethyl thioacetate (5.36 mL, 48.9 mMol) added followed byN,N-diisopropylethylamine (8.4 mL, 48.9 mMol). The resulting solutionwas stirred at room temperature for 2 hours. At the end of this periodthe reaction solution was concentrated under reduced pressure and theresidue dissolved in ethyl acetate. This ethyl acetate solution was thenwashed with 2N-HCl (×2), dried (MgSO₄), filtered and again concentrated.The residual oil was then taken on as such, to the next step.

Invention B-7

Compound of the invention B-7, route B, was prepared from (7a) in asimilar manner to that of invention compound B-1 from compound (7).Yield 6.5 g, 55% based on compound (8).

H¹ --NMR(d⁶ -DMSO): δ=9.55(s, 1H, --NHSO₂ --), 8.50-6.55(m, 10H,Aromatics and --NH₂), 5.18(s, 2H, benzylic --CH₂ --), 3.70(s, 2H, --SCH₂--), 3.17(br.t, 2H, --NHSO₂ CH₂ --), 1.72(m, 2H, --NHSO₂ CH₂ --),1.32-0.80(m, 29H, --NHSO₂ CH₂ CH₂ C₁₄ H₂₉). ##STR14##

SYNTHESIS OF INVENTION COMPOUND B-8--ROUTE B Invention B-8

Invention compound B-8 was prepared from compound (8) (8.2 mMol),2-thioethanol (1.7 mL, 24.5 mMol) and N,N-diisopropylethylamine (4.2 mL,24.5 mMol) in tetrahydrofuran (30 mL) in a similar manner to thatdescribed for compound (9) route B. The product was o purified bypressure chromatography over silica gel with 40% ethyl acetate inheptane as solvent to give B-8 as a foam. Yield 3.5 g, 60%. The H1-nmrand mass spectrum were identical to that of B-8 formed via route A.

The following examples and data further illustrate the invention.Photographic elements were prepared comprising the bleach acceleratingreleasing couplers (BARCs) forming washout dyes as described.

EXAMPLE 1

Illustrative example wherein compounds of the invention are locatedwithin an emulsion layer.

On a cellulose triacetate film support subbed with gelatin, were coatedthe following layers: (amounts are in grams per meter squared).

    ______________________________________                                        Emulsion layer 1                                                                             Gelatin - 3.2; red sensitized                                                 silver bromoiodide (as Ag) -                                                  1.61; cyan image forming                                                      coupler C-1 - 0.75, dispersed                                                 in di-n-butylphthalate,                                                       (1:0.75, by weight); cyan dye                                                 forming DIR coupler                                                           (Development Inhibiting                                                       Releasing Coupler) DC-1 -                                                     0.05, dispersed in N-                                                         butylacetanilide, (1:2 by                                                     weight); BARC(s), as described                                                in TABLE 1, dispersed in N,N-                                                 diethyldodecanamide, (1:2 by                                                  weight); and saponin - 1.5% of                                                melt volume.                                                   Protective Overcoat                                                                          Gelatin - 5.4;                                                                bisvinylsulfonylmethyl ether -                                                2% of total gelatin; and                                                      saponin surfactant - 1.5% of                                                  melt volume.                                                   ______________________________________                                    

Structures of the couplers are as follows: ##STR15##

Strips of each element were exposed to red light through a graduateddensity step tablet and then developed 3.25 minutes at 40° C. in colordeveloper solution CDs1, stopped, washed, bleached using bleachsolutions Bls1, Bls1 modified as described, or Bls2, fixed, washed anddried. Bleach solutions referred to should not be confused with theearlier BLEACH which is a fragment released from coupler (A). Theresidual silver levels were measured by X-ray fluoresence.

    ______________________________________                                        Color Developer, CDs1:                                                        Distilled Water         800    mL                                             Sodium Metabisulfite    2.78   g                                              Sodium Sulfite, anhydrous                                                                             0.38   g                                              Kodak CD-4 (color       4.52   g                                              developer)*                                                                   Potassium Carbonate, anhyd.                                                                           34.3   g                                              Potassium Bicarbonate   2.32   g                                              Sodium Bromide          1.31   g                                              Potassium Iodoide       1.20   mg                                             Hydroxylamine Sulfate (HAS)                                                                           2.41   g                                              Diethylenetriaminepentacetic                                                                          8.43   g                                              acid, pentasodium salt                                                        (40% Soln.)                                                                   Distilled Water         to 1   L                                              Adjust pH to 10.0.                                                            ______________________________________                                        Bleach Solution, Bls1                                                         Distilled water         600    mL                                             Ammonium bromide        150    g                                              Ammonium Ferric EDTA (1.56M,                                                                          175    mL                                             pH 7.05, 44% by weight.                                                       Contains 10% molar excess                                                     EDTA, 3.5% by weight                                                          Glacial acetic acid     9.5    mL                                             Sodium nitrate          35     g                                              Distilled water         to 1   L                                              pH at 26.7° C. 6.00 +/-0.05                                            Adjusted with NH.sub.4 OH or HNO.sub.3.                                       ______________________________________                                        Bleach Solution, Bls2                                                         Gelatin                 0.5    g                                              Sodium persulfate       33.0   g                                              Sodium chloride         15.0   g                                              Sodium dihydrogen phosphate                                                                           9.0    g                                              (anhydrous)                                                                   Distilled water         to 1   L                                              ______________________________________                                         *CD-4 is 4amino-3-methyl-N-ethyl-N-beta-hydroxy-ethylaniline sulfate.    

                                      TABLE 1                                     __________________________________________________________________________    Sensitometric And Bleaching Data                                                          % Silver                                                                             Δγ.sup.b                                                               Change in                                                                             % Silver                                                  Develop-                                                                             (Using                                                                             Speed   Remaining                                                 ment Increase                                                                        Bleach                                                                             (ΔlogE).sup.c                                                                   After 3 Mins in                               BARC   Level.sup.a                                                                        at Mid-Scale                                                                         Solution                                                                           (Using Bleach                                                                         Modified Bleach                               Compound                                                                             (mg/m.sup.2)                                                                       (No Bleach)                                                                          Bls1)                                                                              Solution Bls1)                                                                        Solution, Bls1.sup.d                          __________________________________________________________________________    Comparison                                                                           31.2 33     0.25 +0.13   22                                            Cm-1   62.4 50     0.39 +0.17   19                                            B-1    40.1 34     0.18 +0.05   22                                                   80.2 66     0.31 +0.04   18                                            B-2    37.7 28     0.24 -0.03   28                                                   75.4 49     0.36 -0.06   25                                            Comparison                                                                           31.2 31     0.19 +0.07   20                                            Cm-1   62.4 67     0.42 +0.17   18                                            B-3    37.0 16     0.22 -0.06   24                                                   74.0 35     0.30 -0.07   22                                            B-4    38.5 32     0.17 +0.02   20                                                   77.0 42     0.25 +0.01   21                                                                            Bleach                                                                        Solution Bls2                                 Comparison                                                                           33.4 14     0.14 -0.02   71                                            Cm-2   66.8 19     0.27 -0.06   29                                            B-5    41.5 76     0.66 -0.12   20                                                   83.0 63     0.59 -0.09     2                                           B-6    42.3 47     0.39 -0.09   25                                                   84.6 45     0.31 -0.04    5                                            __________________________________________________________________________     .sup.a These numbers represent two coating levels, 53.8 and 107.6             μMole/m.sup.2.                                                             .sup.b Change in contrast relative to analogous coating containing no         Barc.                                                                         .sup.c Speed relative to analogous coating containing no Barc.                .sup.d Bleach solution Bls1 to which 30.0 g/L of potassium bromide was        added, the resulting solution diluted 1:1 with water;                         ##STR16##                                                                

Structures of the couplers are as follows: ##STR17##

In Example 1, table 1, it can be seen that compounds of the inventionB-1 and B-2, release a bleaching fragment which gives desired bleachingand contrast increases without undesired large speed increases observedwith comparison compound Cm-1. The large speed increase associated withCm-1 is due to the formation of cyan dye which does not wash out of theelement.

Table 1 also shows two variations in bleaching fragment both of whichcontain a carboxylic acid group, released from B-3 and B-4. Both givethe desired increases in contrast and bleaching performance similar toB-1 and B-2. They do not show the large speed increases associated withthe comparison compound Cm-1.

Finally, Table 1 shows two variations in bleaching fragment containingdifferent amine groups and released from B-5 and B-6. In bleachingsolutions based on persulfate as described in Bls2, amine containingbleaching fragments are more effective at promoting bleaching thancarboxylic acid containing bleaching fragments. B-5 and B-6 provideeffective contrast increases and bleaching performance without thedisadvantages associated with the non-washout nature of the dye formedfrom Cm-2.

EXAMPLE 2

Illustrative example wherein compounds of the invention are located inan interlayer, (between imaging layers).

On a cellulose triacetate film support subbed with gelatin, were coatedthe following layers: (amounts are in grams per meter squared, unlessnoted).

    ______________________________________                                        Antihalation layer                                                                        Gelatin - 2.44; and grey                                                      collodal silver - 0.32.                                           Interlayer B                                                                              Gelatin - 0.65; and S-1 -                                                     0.108 Mol/m.sup.2  or BARC(s) -                                               0.108 Mole/m.sup.2, as described in                                           TABLE 2, dispersed in N,N-                                                    diethyldodecanamide, (1:2).                                       Emulsion layer 1:                                                                         Gelatin - 2.15; green                                                         sensitized                                                        (Green Record)                                                                            silver bromoiodide (as Ag) -                                                  1.07; magenta image forming                                                   coupler M-1 - 0.32, dispersed                                                 in dibutylphthalate, (1:1/2);                                                 and magenta dye forming DIR                                                   coupler (Development                                                          Inhibiting Releasing Coupler)                                                 DM-1 - 0.02, dispersed in                                                     dibutylphthalate, (1:2).                                          Interlayer A                                                                              Gelatin - 0.65; and S-1 -                                                     0.108 Mol/m.sup.2  or BARC(s) -                                               0.108 Mole/m.sup.2, as described in                                           TABLE 2, dispersed in N,N-                                                    diethyldodecanamide, (1:2).                                       Emulsion layer 2                                                                          Gelatin - 2.42; blue                                                          sensitized                                                        (Blue Record)                                                                             silver bromoiodide (as Ag) -                                                  0.91; yellow image forming                                                    coupler Y-1 - 0.75, dispesed                                                  in dibutylphthalate, (1:1/3);                                                 and yellow dye forming DIAR                                                   coupler (Development                                                          Inhibiting Releasing Coupler)                                                 DY-1 - 0.05, dispersed in                                                     dibutylphthalate, (1:1/2).                                        Overcoat    Gelatin -.2.7; and bisvinylsulfonylmethyl                                     ether - 1.75% total gelatin.                                      ______________________________________                                    

Structures of the couplers, not already described in Example 1, are asfollows: ##STR18##

Strips of each element were exposed to white light through a graduateddensity step tablet and then developed 3.25 minutes at 40° C. in thecolor developer solution CDs1, described, stopped, washed, bleachedusing bleach solutions, Bls2, Bls3, and modified bleach solutions Bls1and Bls3 as described, fixed, washed and dried.

    ______________________________________                                        Bleach Solution, Bls3                                                         ______________________________________                                        Distilled water          600    mL                                            Ammonium bromide         50.0   g                                             1,3-                                                                          Propanediaminetetraacetic                                                                              30.27  g                                             acid                                                                          Ammonium hydroxide (28%  35.20  g                                             ammonia)                                                                      Ferric nitrate nonahydrate                                                                             36.40  g                                             Glacial acetic acid      26.50  g                                             1,3-Diamino-2-                                                                propanoltetraacetic acid                                                      (Rexpronol Acid, Grace)  1.0    g                                             Ammonmium ferric EDTA    149.0  g                                             (1.56M, pH 7.05, 44% wgt.)                                                    (contains 10% molar excess                                                    EDTA, 3.5% wgt.)                                                              Distilled water to make  1.0    L                                             pH at 26.7° C. 5.25 +/-0.10                                            Adjusted pH with NH.sub.4 OH or HNO.sub.3.                                    ______________________________________                                    

                                      TABLE 2                                     __________________________________________________________________________                                      % Silver                                           Blue Record Green Record   Remaining.sup.a                                    (Using Bleach Solution                                                                    (Using Bleach Solution                                                                       (3 Mins. In Bleach                          BARC   Bls3)       Bls3)          Soln.sup.b)                                 Cpd.                                                                              Loc.sup.c                                                                        .sup.D min                                                                       Δγ.sup.d                                                              (Δlog E).sup.e                                                               .sup.D min                                                                       Δγ.sup.d                                                              (Δlog E).sup.e                                                               RD.sup.f                                                                         (1)                                                                              (2) (3)                                  __________________________________________________________________________    None                                                                              A/B                                                                              0.178                                                                            --  --   0.347                                                                            --  --   0.175                                                                            6.0                                                                              65.3                                                                              7.3                                  S-1.sup.g                                                                     Cm-1                                                                              A  0.136                                                                            +0.02                                                                             -0.08                                                                              0.269                                                                            +0.66                                                                             -0.10                                                                              0.359                                                                            1.1                                                                              65.5                                                                              1.6                                      B  0.141                                                                            -0.03                                                                             -0.13                                                                              0.296                                                                            +0.61                                                                             -0.14                                                                              0.369                                                                            1.6                                                                              94.7                                                                              1.5                                  B-1 A  0.137                                                                            +0.03                                                                             -0.10                                                                              0.275                                                                            +0.47                                                                             -0.11                                                                              0.145                                                                            1.1                                                                              65.3                                                                              1.6                                      B  0.139                                                                            -0.03                                                                             -0.12                                                                              0.280                                                                            +0.49                                                                             -0.12                                                                              0.181                                                                            0.7                                                                              93.5                                                                              0.3                                  B-2 A  0.164                                                                            -0.01                                                                             -0.05                                                                              0.300                                                                            +0.11                                                                             -0.05                                                                              0.150                                                                            7.3                                                                              64.2                                                                              5.0                                      B  0.146                                                                            -0.06                                                                             -0.10                                                                              0.304                                                                            +0.18                                                                             -0.09                                                                              0.148                                                                            3.3                                                                              95.2                                                                              1.5                                  B-5 A  0.142                                                                            +0.13                                                                             -0.05                                                                              0.302                                                                            +0.25                                                                             -0.05                                                                              0.142                                                                            2.4                                                                              4.2 2.4                                  __________________________________________________________________________     ##STR19##                                                                     .sup.b The following bleach solutions or modified bleach solutions were       used: (1) Bleach solution Bls1 to which 30.0 g/L of potassium bromide was     added, the resulting solution diluted 1:1 with water; (2) Bleach solution     Bls2: and (3) Bleach solution Bls3 diluted 7:3 with water.                    .sup.c Interlayer (A or B), in which Barc compounds of the invention are      located.                                                                      .sup.d Change in contrast.                                                    .sup.e Speed relative to control, see footnote g.                             .sup.f Red density measured at maximum exposure.                              .sup.g This is the control, with 0.108 mol/m.sup.2 of S1 only, in both        Interlayers A and B.                                                     

From Table 2 it can be seen that photographic elements containingcompounds of the invention B-1, B-2 and B-5 have less red density atD_(max), than the comparison Cm-1, showing that during processing, thedyes formed from the compounds of the invention, are washing out of thephotographic elements. This in not the case for Cm-1.

Table 2 also shows that photographic elements containing compounds ofthe invention have lower D_(min) values than those containing S-1. Thisshows that compounds of the invention are very effective scavangers ofoxidized color developer.

Changes in speed and contrast were generally less with compounds of theinvention or comparison compounds when they were coated in interlayers,see Table 1, compared with emulsion containing layers.

Compounds of the invention give excellent bleaching when coated ininterlayers.

Other compounds of the invention are as follows: ##STR20##

Other compounds of the invention are as follows: ##STR21##

This invention has been described in detail with particular reference topreferred embodiments thereof, but it will be understood that variationsand modifications can be effected within the spirit and scope of theinvention.

What is claimed is:
 1. A color photographic element comprising a supportbearing at least one photographic silver halide emulsion layer, an imagemodifying coupler, and a coupler (A) capable of forming a compound uponreaction with oxidized developer that is washed out of the photographicelement upon processing or forms a compound that washes out afterfurther reaction and is capable of releasing a bleach accelerator group,wherein the coupler (A) is represented by the formula ##STR22## whereinR³ is selected from the group consisting of hydrogen, substituted orunsubstituted alkyl containing 1-5 carbon atoms and substituted orunsubsubstituted aryl containing 6-8 carbon atoms where the substitutedor unsubstituted alkyl or aryl is a solubilizing group or contains asolubilizing group;R⁴ is selected from hydrogen, --Cl, --NO₂, --OCH₃,--NHSO₂ R⁵, --NHCOR⁵, --SO₂ NHR⁵, --CONHR⁵, --CO₂ R₅, or --COR⁵ ; R⁵ isselected from the group consisting of hydrogen, substituted orunsubstituted alkyl containing 1-5 carbon atoms and substituted orunsubsubstituted aryl containing 6-8 carbon atoms where the substitutedor unsubstituted alkyl or aryl is a solubilizing group or contains asolubilizing group; Q is selected from O (oxygen), S (sulfur), or N(nitrogen); R⁶ is hydrogen or a substituent selected from substituted orunsubstituted alkyl and substituted or unsubstituted aryl, nitro, amino,substituted amino, carboxylic acid, sulfonic acid, methoxy, chloro,bromo, ester group, keto group, --NHCOCH₃, --CONHCH₃, --NHSO₂ CH₃, and--SO₂ NHCH₃ ; R⁷, and R⁸ are selected from hydrogen, substituted orunsubstituted alkyl, and substituted or unsubstituted aryl; R⁹ isunsubstituted or substituted alkyl or substituted or unsubstituted aryl;Z¹ represents the atoms necessary to complete a 5 or 6 member aryl orheterocyclic group; w is 0, 1, 2 or 3; n is 0, 1 or 2; BLEACH is ableach accelerator group represented by the formula:

    --S--R.sup.13 --R.sup.14

wherein:R¹³ is an unsubstituted or substituted alkylene containing 1 to8 carbon atoms; and R¹⁴ is a water solubilizing group comprising amorpholino group or a group having the structure

    --NR.sup.14a R.sup.14b

wherein:R^(14a) is hydrogen or alkyl of 1 to 4 carbon atoms, R^(14b) isalkyl of 1 to 4 carbon atoms, the total carbons in R^(14a) and R^(14b)is not more than 8, and R^(14a) and R^(14b) further being capable oftogether forming a ring; and at least one of R⁶, R⁷, R⁸, or R⁹ containsa photographic ballast.
 2. A color photographic element as in claim 1comprising a supportat least one red sensitive photographic silverhalide emulsion layer comprising at least one cyan image dye-formingcoupler; at least one green sensitive photographic silver halideemulsion layer comprising at least one magenta image dye-formingcoupler; and, at least one blue sensitive photographic silver halideemulsion layer comprising at least one yellow image dye-forming coupler;and, at least one non-imaging layer; and at least one of the layerscomprises at least one coupler (A) as defined in claim
 1. 3. Thephotographic element in accordance with claim 1 wherein coupler (A) islocated in an imaging layer.
 4. The photographic element in accordancewith claim 1 wherein coupler (A) is located in an interlayer between twoimaging layers.
 5. The photographic element in accordance with claim 1wherein coupler (A) is located in an interlayer between an imaging layerand the support.
 6. A process of forming an image in an exposedphotographic element as defined in claim 1 comprising developing thephotographic element with a color developer.